CN103619827B - Make the method that the compositions of carbohydrate containing is dehydrated - Google Patents
Make the method that the compositions of carbohydrate containing is dehydrated Download PDFInfo
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- CN103619827B CN103619827B CN201280029097.8A CN201280029097A CN103619827B CN 103619827 B CN103619827 B CN 103619827B CN 201280029097 A CN201280029097 A CN 201280029097A CN 103619827 B CN103619827 B CN 103619827B
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- 238000000034 method Methods 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 125000000837 carbohydrate group Chemical group 0.000 title 1
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 50
- 239000006200 vaporizer Substances 0.000 claims description 76
- 239000002608 ionic liquid Substances 0.000 claims description 75
- 239000002904 solvent Substances 0.000 claims description 51
- 235000014633 carbohydrates Nutrition 0.000 claims description 48
- 238000007599 discharging Methods 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 230000018044 dehydration Effects 0.000 claims description 30
- 238000006297 dehydration reaction Methods 0.000 claims description 30
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 21
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 20
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 13
- 229930091371 Fructose Natural products 0.000 claims description 12
- 239000005715 Fructose Substances 0.000 claims description 12
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- 229920001542 oligosaccharide Polymers 0.000 claims description 11
- 150000002482 oligosaccharides Chemical class 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 150000002772 monosaccharides Chemical class 0.000 claims description 7
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 6
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical group [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 4
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 150000002016 disaccharides Chemical class 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- MFCKWROQZDZCDJ-UHFFFAOYSA-N 2-(1-ethyl-3-methyl-2h-imidazol-2-yl)acetic acid Chemical compound CCN1C=CN(C)C1CC(O)=O MFCKWROQZDZCDJ-UHFFFAOYSA-N 0.000 claims description 3
- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- GZCGUPFRVQAUEE-UHFFFAOYSA-N 2,3,4,5,6-pentahydroxyhexanal Chemical compound OCC(O)C(O)C(O)C(O)C=O GZCGUPFRVQAUEE-UHFFFAOYSA-N 0.000 claims description 2
- AEMOLEFTQBMNLQ-UHFFFAOYSA-N 3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound OC1OC(C(O)=O)C(O)C(O)C1O AEMOLEFTQBMNLQ-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001320 aldopentoses Chemical class 0.000 claims description 2
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- -1 halogen ion Chemical class 0.000 description 30
- 150000001768 cations Chemical class 0.000 description 27
- 150000001450 anions Chemical class 0.000 description 26
- 239000000047 product Substances 0.000 description 24
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 229910052909 inorganic silicate Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000005842 heteroatom Chemical group 0.000 description 8
- 150000002402 hexoses Chemical class 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 150000004676 glycans Chemical class 0.000 description 6
- 229920001282 polysaccharide Polymers 0.000 description 6
- 239000005017 polysaccharide Substances 0.000 description 6
- 238000007614 solvation Methods 0.000 description 6
- 150000003512 tertiary amines Chemical class 0.000 description 6
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 238000007600 charging Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- DPBLXKKOBLCELK-UHFFFAOYSA-N n-pentylamine Natural products CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229910020489 SiO3 Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000002678 macrocyclic compounds Chemical class 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLJSMWDFUFADIA-UHFFFAOYSA-N 1,3-diethylimidazol-1-ium Chemical compound CCN1C=C[N+](CC)=C1 XLJSMWDFUFADIA-UHFFFAOYSA-N 0.000 description 2
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical class CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 2
- FROQVHAYMSVXTG-UHFFFAOYSA-N 1-hexyl-2h-pyridine Chemical compound CCCCCCN1CC=CC=C1 FROQVHAYMSVXTG-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- 229910003813 NRa Inorganic materials 0.000 description 2
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- KLVOSHOFGYMCCP-UHFFFAOYSA-N n,n-di(propan-2-yl)butan-1-amine Chemical compound CCCCN(C(C)C)C(C)C KLVOSHOFGYMCCP-UHFFFAOYSA-N 0.000 description 2
- HTDCNKTXDLRMHZ-UHFFFAOYSA-N n,n-dibutylcyclohexanamine Chemical compound CCCCN(CCCC)C1CCCCC1 HTDCNKTXDLRMHZ-UHFFFAOYSA-N 0.000 description 2
- UPNQFYMXRSHQBY-UHFFFAOYSA-N n,n-diethyl-2-methylpropan-2-amine Chemical compound CCN(CC)C(C)(C)C UPNQFYMXRSHQBY-UHFFFAOYSA-N 0.000 description 2
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- 238000010025 steaming Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
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- CVHZOJJKTDOEJC-UHFFFAOYSA-M 1,1-dioxo-1,2-benzothiazol-3-olate Chemical compound C1=CC=C2C([O-])=NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-M 0.000 description 1
- KCUGPPHNMASOTE-UHFFFAOYSA-N 1,2,3-trimethylimidazol-1-ium Chemical compound CC=1N(C)C=C[N+]=1C KCUGPPHNMASOTE-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- DWXPYPYNNXEZIP-UHFFFAOYSA-N 1,3,4,5-tetramethyl-2h-imidazole Chemical class CN1CN(C)C(C)=C1C DWXPYPYNNXEZIP-UHFFFAOYSA-N 0.000 description 1
- CDIWYWUGTVLWJM-UHFFFAOYSA-N 1,3,4-trimethylimidazol-1-ium Chemical compound CC1=C[N+](C)=CN1C CDIWYWUGTVLWJM-UHFFFAOYSA-N 0.000 description 1
- VRQAYEKWRUXKLP-UHFFFAOYSA-N 1,4,5-trimethyl-3-octyl-2h-imidazole Chemical compound CCCCCCCCN1CN(C)C(C)=C1C VRQAYEKWRUXKLP-UHFFFAOYSA-N 0.000 description 1
- JVNKHQNLEURZFW-UHFFFAOYSA-N 1,4-dimethyl-3-octyl-2h-imidazole Chemical compound CCCCCCCCN1CN(C)C=C1C JVNKHQNLEURZFW-UHFFFAOYSA-N 0.000 description 1
- SZQCPPRPWDXLMM-UHFFFAOYSA-N 1,4-dimethylpyrazole Chemical compound CC=1C=NN(C)C=1 SZQCPPRPWDXLMM-UHFFFAOYSA-N 0.000 description 1
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- ARJRHPLYUDOSCK-UHFFFAOYSA-N 1-butan-2-ylpiperidine Chemical class CCC(C)N1CCCCC1 ARJRHPLYUDOSCK-UHFFFAOYSA-N 0.000 description 1
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- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- AXWLKJWVMMAXBD-UHFFFAOYSA-N 1-butylpiperidine Chemical compound CCCCN1CCCCC1 AXWLKJWVMMAXBD-UHFFFAOYSA-N 0.000 description 1
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- FZCIPZVRXZEKLV-UHFFFAOYSA-N 1-dodecyl-2-methyl-2h-pyridine Chemical compound CCCCCCCCCCCCN1C=CC=CC1C FZCIPZVRXZEKLV-UHFFFAOYSA-N 0.000 description 1
- YIOGLGOXZGOFCZ-UHFFFAOYSA-N 1-dodecyl-2h-pyridine Chemical compound CCCCCCCCCCCCN1CC=CC=C1 YIOGLGOXZGOFCZ-UHFFFAOYSA-N 0.000 description 1
- GCRXLBLHBKCPHD-UHFFFAOYSA-N 1-dodecyl-3-ethyl-2-methyl-2H-pyridine Chemical compound C(CCCCCCCCCCC)N1C(C(=CC=C1)CC)C GCRXLBLHBKCPHD-UHFFFAOYSA-N 0.000 description 1
- DVNFMHWKXQEEAH-UHFFFAOYSA-N 1-dodecyl-3-methyl-2h-imidazole Chemical compound CCCCCCCCCCCCN1CN(C)C=C1 DVNFMHWKXQEEAH-UHFFFAOYSA-N 0.000 description 1
- JMTFLSQHQSFNTE-UHFFFAOYSA-N 1-dodecylimidazole Chemical class CCCCCCCCCCCCN1C=CN=C1 JMTFLSQHQSFNTE-UHFFFAOYSA-N 0.000 description 1
- OIKCWPURLYQCEQ-UHFFFAOYSA-N 1-ethyl-2-methyl-2h-pyridine Chemical compound CCN1C=CC=CC1C OIKCWPURLYQCEQ-UHFFFAOYSA-N 0.000 description 1
- UCRIXEWTILHNCG-UHFFFAOYSA-N 1-ethyl-2h-pyridine Chemical compound CCN1CC=CC=C1 UCRIXEWTILHNCG-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 1
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical compound CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 description 1
- NWRUFJHICAREBX-UHFFFAOYSA-N 1-pentylpyrrolidine Chemical compound CCCCCN1CCCC1 NWRUFJHICAREBX-UHFFFAOYSA-N 0.000 description 1
- KXIXHISTUVHOCY-UHFFFAOYSA-N 1-propan-2-ylpiperidine Chemical class CC(C)N1CCCCC1 KXIXHISTUVHOCY-UHFFFAOYSA-N 0.000 description 1
- RSVIUCBJPRWLIZ-UHFFFAOYSA-N 1-tert-butylpiperidine Chemical compound CC(C)(C)N1CCCCC1 RSVIUCBJPRWLIZ-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 1
- ZJQSJWCXSGAZFQ-UHFFFAOYSA-N 2-ethyl-1-hexyl-2H-pyridine Chemical compound C(CCCCC)N1C(C=CC=C1)CC ZJQSJWCXSGAZFQ-UHFFFAOYSA-N 0.000 description 1
- HBGVDRFDCWCCMS-UHFFFAOYSA-N 2-ethyl-1-methyl-2H-pyridine Chemical compound CCC1C=CC=CN1C HBGVDRFDCWCCMS-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- RDTIFYBSPQERAS-UHFFFAOYSA-O 3,4,5-trimethyl-1h-imidazol-3-ium Chemical compound CC=1NC=[N+](C)C=1C RDTIFYBSPQERAS-UHFFFAOYSA-O 0.000 description 1
- WVTUYDXGRBJVGK-UHFFFAOYSA-N 3-ethyl-1-hexyl-2-methyl-2H-pyridine Chemical compound C(CCCCC)N1C(C(=CC=C1)CC)C WVTUYDXGRBJVGK-UHFFFAOYSA-N 0.000 description 1
- ZZKDGABMFBCSRP-UHFFFAOYSA-N 3-ethyl-2-methylpyridine Chemical compound CCC1=CC=CN=C1C ZZKDGABMFBCSRP-UHFFFAOYSA-N 0.000 description 1
- FDHGUCPWMSEFHX-UHFFFAOYSA-N 4-butan-2-ylmorpholine Chemical compound CCC(C)N1CCOCC1 FDHGUCPWMSEFHX-UHFFFAOYSA-N 0.000 description 1
- LMRKVKPRHROQRR-UHFFFAOYSA-N 4-butylmorpholine Chemical compound CCCCN1CCOCC1 LMRKVKPRHROQRR-UHFFFAOYSA-N 0.000 description 1
- IERWMZNDJGYCIA-UHFFFAOYSA-N 4-pentylmorpholine Chemical compound CCCCCN1CCOCC1 IERWMZNDJGYCIA-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- YMRPKBLFDBUOAJ-UHFFFAOYSA-N 5-butyl-2-methyl-1h-imidazole Chemical class CCCCC1=CN=C(C)N1 YMRPKBLFDBUOAJ-UHFFFAOYSA-N 0.000 description 1
- IAFQBDQXXOVBHC-UHFFFAOYSA-N 5-ethyl-1,2-dimethyl-2h-pyridine Chemical compound CCC1=CN(C)C(C)C=C1 IAFQBDQXXOVBHC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical class C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- GTPMHAMQFBAQBM-UHFFFAOYSA-N N1=CC=CC=C1.C(CCCC)N1CCNCC1 Chemical compound N1=CC=CC=C1.C(CCCC)N1CCNCC1 GTPMHAMQFBAQBM-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical class C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical class C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 101100434205 Solanum tuberosum AC75 gene Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical class OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N mono-n-propyl amine Natural products CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- HNIMBAXJIKTYOV-UHFFFAOYSA-N n,n-di(propan-2-yl)pentan-1-amine Chemical compound CCCCCN(C(C)C)C(C)C HNIMBAXJIKTYOV-UHFFFAOYSA-N 0.000 description 1
- ORSUTASIQKBEFU-UHFFFAOYSA-N n,n-diethylbutan-1-amine Chemical compound CCCCN(CC)CC ORSUTASIQKBEFU-UHFFFAOYSA-N 0.000 description 1
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 description 1
- BVUGARXRRGZONH-UHFFFAOYSA-N n,n-diethyloctan-1-amine Chemical compound CCCCCCCCN(CC)CC BVUGARXRRGZONH-UHFFFAOYSA-N 0.000 description 1
- VNTWDXBPWOKDLY-UHFFFAOYSA-N n-benzyl-n-butylaniline Chemical compound C=1C=CC=CC=1N(CCCC)CC1=CC=CC=C1 VNTWDXBPWOKDLY-UHFFFAOYSA-N 0.000 description 1
- HSZCJVZRHXPCIA-UHFFFAOYSA-N n-benzyl-n-ethylaniline Chemical compound C=1C=CC=CC=1N(CC)CC1=CC=CC=C1 HSZCJVZRHXPCIA-UHFFFAOYSA-N 0.000 description 1
- ZWRDBWDXRLPESY-UHFFFAOYSA-N n-benzyl-n-ethylethanamine Chemical compound CCN(CC)CC1=CC=CC=C1 ZWRDBWDXRLPESY-UHFFFAOYSA-N 0.000 description 1
- OJKDJKUSLNKNEL-UHFFFAOYSA-N n-benzyl-n-propan-2-ylaniline Chemical compound C=1C=CC=CC=1N(C(C)C)CC1=CC=CC=C1 OJKDJKUSLNKNEL-UHFFFAOYSA-N 0.000 description 1
- BBDGYADAMYMJNO-UHFFFAOYSA-N n-butyl-n-ethylbutan-1-amine Chemical compound CCCCN(CC)CCCC BBDGYADAMYMJNO-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical class C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
Abstract
The present invention relates to a kind of method that compositions making carbohydrate containing is dehydrated.
Description
The present invention relates to a kind of method that compositions making carbohydrate containing is dehydrated.
By in biomass material economic space structure valuable material, various carbohydrate sources the dehydration obtained is produced
Thing especially has the biggest potentiality.Hexose is to be distributed the widest monosaccharide in nature, and D fructose and D-Glucose especially can be to fill
The amount of foot and the best condition obtain.Hexose is that one has extra high desired side to the conversion of furan product
Method.In this case, 5-Hydroxymethylfurfural (5-HMF), the i.e. dehydration product of hexose especially have pivotal role.It is especially
Can be used as the starting point of synthetic drug, polymer and macrocyclic compound.Its derivant includes such as 2,5-furfuryl group diamidogen, 2,5-bran
Group diisocyanate and 5-hydroxymethyl furfurylidene ester, it can be used for producing polyester, polyamide and polyurethane.
Avelino Corma, Sara Iborra and Alexandra Velty at Chem.Rev.2007,107,2411-
The various chemistry routes that biomass are changed into chemicals are described in 2502, especially under 2.2.1 point, the dehydration of monosaccharide,
The most acid catalyzed fructose is dehydrated.The shortcoming of the method implemented in the presence of water is that the 5-HMF of gained occurs partially dehydrated.
This shortcoming such as by using the 5-HMF of organic solvent extraction gained simultaneously, or can be dehydrated and keep away in organic solvent
Exempt from.Such as, when implementing reaction at DMSO, it is thus achieved that good productivity.But, this modification is disadvantageous in that DMSO only may be used
Difficulty separate with 5-HMF, and form poisonous sulfur byproduct species.It is mentioned that at 1-butyl-3-Methylimidazole.Tetrafluoro boron
Hydrochlorate, i.e. implements this reaction in ion solvent.At 80 DEG C after the response time of 3 hours, can obtain with the productivity of 50%
5-HMF.By using DMSO as cosolvent and 24 hours will be extended to the response time, the productivity raising to 80% can be obtained.
Xinli Tong, Yang Ma and Yongdan Li is at Applied Catalysis A:Genera385 (2010) 1-
13 describe use saccharide produces furan chemical, especially by various carbohydrate sources such as fructose, glucose, polysaccharide and
Biomass material synthesis 5-Hydroxymethylfurfural (5-HMF), 2,5-furandicarboxylic acid (2,5-FDCA), 2,5-diformyl furan
(2,5-DFF), 2,5-double (hydroxymethylfurans (2,5-BHF) and 2,5-dimethyl furan (2,5-DMF).Describe based on respectively
Plant catalyst, such as mineral acid, organic acid, solid acid and the method containing metallic catalyst.
Yu Su, Heather M.Brown, Xiwen Huang, Xiao-dong Zhou, James E.Amonette and
Z.Conrad Zhang at Applied Catalysis A:General, volume 361, the 1-2 phase, on June 20th, 2009,
117-122 page describes cellulose to the single stage conversion of 5-HMF.It is dissolved in 1-ethyl-3-methylimidazoleChloride ([EMIM]
Cl) the metal chloride pairing (CuCl in2And CrCl2) at a temperature of 80-120 DEG C, it is catalyzed described reaction with high-purity.At this
In the case of Zhong, faster than acid catalyzed reaction more than 10 times of the depolymerization of cellulose.
Ken-ichi Shimizu, Rie Uozumi and Atsushi Satsuma is at Catalysis
Communications10 (2009), the 1849-1853 page describe a kind of improvement at solid acid catalyst such as heteropoly acid, boiling
In the presence of stone and acid ion exchange, by continuously from reactant mixture, remove water with the pressure reduced slightly and by fructose
The method preparing 5-HMF.
Persistently need to be prepared the economic means of dehydration product by various carbohydrate sources.These are intended to quickly, even
Continuous and/or selectivity preparation is possibly realized.It is especially intended to be suitable to be prepared 5-by hexose and the carbohydrate source comprising hexose
Hydroxymethyl furfural (5-HMF).
It is surprisingly found that this purpose to realize by the following method: wherein to comprising at least one low boiling point solvent and extremely
The compositions of the carbohydrate containing of few a kind of ionic liquid carries out being dehydrated and evaporating simultaneously described low boiling point solvent and formed
At least some dehydration product, and from dehydration/evaporation region, be continuously withdrawn gaseous state discharging.
Therefore, the present invention relates to the continuation method that a kind of compositions making carbohydrate containing is dehydrated, comprising:
I) provide and comprise the compositions of following component:
-at least one carbohydrate,
-at least one ionic liquid (IL), and
-at least one has the solvent (LM) of the boiling point being up to 120 DEG C under normal pressure (1013 millibars)；
Ii) compositions of step i) fed in vaporizer and make it the temperature of 100-300 DEG C and be up to 500 millibars
Pressure under react and evaporate；
Iii) from described vaporizer, take out the gaseous state discharging comprising dehydration product, and taking-up comprises at least one ionic liquid
The liquid discharging of body；
Iv) make described gaseous state discharging condensation and it is separated described dehydration product.
In each embodiment of the inventive method being described below, one or more in the following point of the method for the present invention
For be favourable:
-short residence time in vaporizer；
-continuation method；
-need not catalyst；
-be dehydrated in the presence of ion solvent and the having of separating by the gained dehydration product in the aqueous gaseous stream of distillation
Profit combination；
-owing to discharging together as gaseous state discharging with solvent (LM), gained dehydration product is with ionic liquid (IL) well
Separate；
-the ionic liquid (IL) that is present in liquid discharging is substantially free of evaporation the solvent (LM) discharged with gaseous state；
-the ionic liquid (IL) that is present in liquid discharging is substantially free of in dehydration formation water, and described water steams
Send out and discharge with gaseous state；
-avoid the inactivation of ionic liquid (IL) assembled and cause due to water.
The most only comprise the percentage ratio of one digit number in the gaseous state discharging taken out from vaporizer even from the inventive method
The dehydration product of (one figure percentage), the inventive method is also favourable than known discontinuous method.Therefore, with
The time of staying of the many hour of perception method is compared, and the time of staying in vaporizer is only the several seconds to several minutes.Therefore, originally
The space-time yield of inventive method is high.Short residence time, in gaseous stream, quickly remove gained dehydration product and the coldest
Solidifying energy controls the method for as the dehydration product of target components.In contrast, it is known that discontinuous method cause lasting again
Aquation and the balance of various enolate, and therefore form the production spectra of complexity.
The inventive method can be prepared dehydration product by the raw material comprising carbohydrate, wherein can not use prior art institute
The known conventional catalyst for this dehydration.Additionally, it is not essential that the carbon containing aquation for dehydration of the present invention
The compositions of compound and mineral acid, organic acid, solid acid catalyst such as heteropoly acid, zeolite and acid ion exchange and contain metal
Catalyst contact.
In the context of the present invention, wording " solvation " expression changes into liquid and includes herein forming carbohydrate containing
The solution of raw material and change into Solvation State unlike this.If polysaccharide, cellulosic material or ligno-cellulosic
Material changes into Solvation State, and the most each polymer molecule need not be surrounded completely by solvate sheath.It is essential that polymer
Liquid is changed into due to solvation.Therefore, in the present invention, solvation material is also colloid solution, fine dispersion, gel
Deng.
Compositions (step i of carbohydrate containing is provided)
Preferably, the content of the raw material of the carbohydrate containing of the compositions provided in step i) is 1-20 weight %, especially
Preferably 2-15 weight %, gross weight based on described compositions.
In the context of the present invention, wording " compositions of carbohydrate containing " include comprising monosaccharide, oligosaccharide, polysaccharide and
The compositions of its mixture.Wording " oligosaccharide " refers to the carbohydrate with 2-6 monosaccharide unit.Wording " polysaccharide " refers to tool
There is the carbohydrate more than 6 monosaccharide units.The prototypical member of polysaccharide for example, cellulose, starch and glycogen.
In the first preferred embodiment, the raw material of described carbohydrate containing is selected from list-and/or oligosaccharide.Described carbon containing
The raw material of hydrate is especially selected from list-and/or disaccharide.
Preferably, described list-and/or oligosaccharide are selected from:
-aldopentose,
-aldohexose,
-ketohexose,
-derived from the disaccharide of aldopentose, aldohexose, ketohexose and mixture thereof, and
-its mixture.
It is particularly preferred that described list-and/or disaccharide are selected from fructose, glucose, sucrose, xylose and mixture thereof.
The preferred embodiment of the inventive method is dehydrated for making fructose to prepare 5-Hydroxymethylfurfural (5-HMF).
The preferred embodiment of the inventive method is dehydrated for making sucrose to prepare 5-Hydroxymethylfurfural (5-HMF).
The preferred embodiment of the inventive method is dehydrated for making xylose to prepare furfural.
In the second preferred embodiment, the raw material of described carbohydrate containing is selected from cellulosic material.
Additionally, also cellulose or the lignocellulose that are adapted as the raw material of the carbohydrate containing of the inventive method are former
The enzymatic hydrolysate of material.
Ionic liquid (IL)
In the context of the present invention, ionic liquid refers at a temperature of less than 180 DEG C for the organic salt of liquid.Excellent
Selection of land, described ionic liquid has less than 150 DEG C, especially preferably less than 120 DEG C, the ion of the fusing point of especially less than 100 DEG C
Liquid.
The ionic liquid being the most in a liquid state such as is described in K.N.Marsh etc., Fluid Phase
Equilibria219 (2004), 3-98 and J.G.Huddleston etc., Green Chemistry2001, in 3,156-164.
Ionic liquid be applicable to the inventive method is described in WO2008/090155 and WO2008/090156, leads to herein
Cross and be incorporated herein by reference.
Ionic liquid exists cation and anion.In this case, the proton in ionic liquid or alkyl can be by
Cation is transferred to anion, thus obtains two neutral molecules.Therefore, in the ionic liquid used by the present invention, can exist
Anion, cation and the balance of neutral molecule formed by it.
Preferably ionic liquid is that cationic nitrogenous component is (such as imidazolesDerivant) and as the halogen ion of anion
Combination.
The suitable compound of the cation suitably forming ionic liquid is such as described in DE10202838A1.These chemical combination
Preferably containing at least one hetero atom of thing, such as 1-10 hetero atom, described hetero atom is preferably selected from nitrogen, oxygen, p and s atom.Excellent
Choosing comprises at least one nitrogen-atoms and the most extra at least one is different from other heteroatomic compounds of nitrogen.Preferably comprise
At least one nitrogen-atoms, particularly preferred 1-10 nitrogen-atoms, particularly 1-5 nitrogen-atoms, very particularly preferably 1-3 nitrogen is former
The compound of son, especially 1 or 2 nitrogen-atoms.Last described nitrogen compound can comprise other of such as oxygen, sulfur and phosphorus atoms
Hetero atom.
The suitable carrier of the positive charge in the cation of the most described ionic liquid of nitrogen-atoms.It is ionic liquid to nitrogen-atoms
For the situation of the positive charge carrier in body cation, cation can be passed through can be first such as in the synthesis of this ionic liquid
On the nitrogen-atoms of amine or azacyclo-quaternized and formed.Quaternized carried out by the protonation of nitrogen-atoms.Depend on used
Protonating agent, it is thus achieved that there is the salt of different anions.Can not quickly form in quaternization process wherein required the moon from
In the case of son, this can be carried out in another synthesis step.Such as, when being initiateed by ammonium halide, described halogenide and road can be made
Lewis acid reacts, and is wherein formed coordination anion by halogenide and lewis acid.Or, it is required anion by halogen ion exchange
It is possible.This can realize via ion-exchanger and formation metal halide precipitate by adding slaine, or passes through
Realize with strong acid displacement halogen ion (discharging halogen acids).Suitably method is such as described in Angew.Chem.2000, and 112,
In the 3926-3945 page and wherein cited document.
Preferably containing at least one 5-6 element heterocycle, particularly has at least one nitrogen-atoms and also can to have an oxygen former
Those compounds of the 5-membered heterocycles of son or sulphur atom.Particularly preferably comprise at least one and there is 1,2 or 3 nitrogen-atoms and one
Those compounds of the 5-6 element heterocycle of sulphur atom or an oxygen atom, very particularly preferably have those of 2 nitrogen-atoms.Enter
The one preferred aromatic heterocycle compounds of step.
Particularly preferred compound is for having less than 1000g/mol, very particularly preferably less than 800g/mol, the least
Those of molal weight in 500g/mol.
Preferably cation is pyridineClass ion.These are especially selected from pyridine2-picoline2-ethyl pyrrole
PyridineAldehydecollidineWith 2-methyl-3-ethylpyridineAnd 1-picoline1-ethylpyridine1-(1-butyl) pyridine1-(1-hexyl) pyridine1-(1-octyl group) pyridine1-(1-hexyl) pyridine1-
(1-octyl group) pyridine1-(1-dodecyl) pyridine1-(1-myristyl) pyridine1-(1-cetyl) pyridine1,2-lutidines1-Ethyl-2-Methyl pyridine1-(1-butyl)-2-picoline(1-is own for 1-
Base)-2-picoline1-(1-octyl group)-2-picoline1-(1-dodecyl)-2-picoline1-(1-
Myristyl)-2-picoline1-(1-cetyl)-2-picoline1-methyl-2-ethylpyridine1,2-
Parvoline1-(1-butyl)-2-ethylpyridine1-(1-hexyl)-2-ethylpyridine1-(1-octyl group)-2-
Ethylpyridine1-(1-dodecyl)-2-ethylpyridine9-(1-myristyl)-2-ethylpyridine1-(1-ten
Six alkyl)-2-ethylpyridine1,2-dimethyl-5-ethylpyridine1,5-diethyl-2-picoline1-(1-
Butyl)-2-methyl-3-ethylpyridine1-(1-hexyl)-2-methyl-3-ethylpyridineWith 1-(1-octyl group)-2-first
Base-3-ethylpyridine1-(1-dodecyl)-2-methyl-3-ethylpyridine1-(1-myristyl)-2-methyl-3-
EthylpyridineWith 1-(1-cetyl)-2-methyl-3-ethylpyridine
Furthermore it is preferred that cation be unsubstituted or substituted pyridazineIon.
Furthermore it is preferred that cation be unsubstituted or substituted pyrimidineIon.
Furthermore it is preferred that cation be unsubstituted or substituted pyrazineIon.
Furthermore it is preferred that cation be unsubstituted or substituted imidazolesIon.Specially suitable imidazolesClass ion
For 1-Methylimidazole.1-ethyl imidazol(e)1-(1-propyl group) imidazoles1-(1-pi-allyl) imidazoles1-(1-butyl)
Imidazoles1-(1-octyl group) imidazoles1-(1-dodecyl) imidazoles1-(1-myristyl) imidazoles1-(1-16
Alkyl) imidazoles1,3-methylimidazole1,3-diethyl imidazolium1-ethyl-3-methylimidazole1-(1-fourth
Base)-3-Methylimidazole.1-(1-butyl)-3-ethyl imidazol(e)1-(1-hexyl)-3-Methylimidazole.(1-is own for 1-
Base)-3-ethyl imidazol(e)1-(1-hexyl)-3-butyl-imidazolium1-(1-octyl group)-3-Methylimidazole.(1-is pungent for 1-
Base)-3-ethyl imidazol(e)1-(1-octyl group)-3-1-Butyl-1H-imidazole1-(1-dodecyl)-3-Methylimidazole.1-(1-
Dodecyl)-3-ethyl imidazol(e)1-(1-dodecyl)-3-1-Butyl-1H-imidazole1-(1-dodecyl)-3-octyl group miaow
Azoles1-(1-myristyl)-3-Methylimidazole.1-(1-myristyl)-3-ethyl imidazol(e)1-(the 1-tetradecane
Base)-3-1-Butyl-1H-imidazole1-(1-myristyl)-3-octylimidazole1-(1-cetyl)-3-Methylimidazole.1-
(1-cetyl)-3-ethyl imidazol(e)1-(1-cetyl)-3-1-Butyl-1H-imidazole1-(1-cetyl)-3-octyl group
ImidazolesDMIZ 1,2 dimethylimidazole1,2,3-tri-methylimidazolium1-ethyl-2,3-methylimidazole1-(1-fourth
Base)-2,3-methylimidazole1-(1-hexyl)-2,3-methylimidazole1-(1-octyl group)-2,3-methylimidazole1,4-methylimidazole1,3,4-tri-methylimidazolium1,4-dimethyl-3-ethyl imidazol(e)3-Methylimidazole.3-ethyl imidazol(e)3-n-pro-pyl imidazoles3-butylimidazolium1,4-dimethyl-3-octylimidazole1,
4,5-tri-methylimidazolium1,3,4,5-tetramethyl imidazoles1,4,5-trimethyl-3-ethyl imidazol(e)1,4,5-front three
Base-3-1-Butyl-1H-imidazole1,4,5-trimethyl-3-octylimidazole1-acrylate-1-alkene-3-base-3-Methylimidazole.With 1-acrylate-
1-alkene-3-base-3-1-Butyl-1H-imidazoleThe imidazoles being particularly suitableIon (IVe) is 1,3-diethyl imidazolium1-ethyl-
3-Methylimidazole.1-normal-butyl-3-Methylimidazole.。
Furthermore it is preferred that cation be unsubstituted or substituted pyrazolesIon.Particularly preferred pyrazolesClass ion
For pyrazolesWith 1,4-dimethyl pyrazole
Furthermore it is preferred that cation be unsubstituted or substituted dihydropyazoloIon.
Furthermore it is preferred that cation be unsubstituted or substituted imidazolineIon.
Furthermore it is preferred that cation be unsubstituted or substituted thiazoleIon.
Furthermore it is preferred that cation be unsubstituted or substituted 1,2,4-triazolesIon.
Furthermore it is preferred that cation be unsubstituted or substituted pyrrolidineIon.
Furthermore it is preferred that cation be unsubstituted or substituted imidazolidineIon.
Furthermore it is preferred that cation be unsubstituted or substituted ammonium ion.By deriving by it with described group R is quaternized
The tertiary amine example of quaternary ammonium ion is diethyl n-butylamine, diethyl tert-butylamine, diethyl n-pentyl amine, diethylhexyl
Amine, diethyl octyl amine, diethyl (2-ethylhexyl) amine, diη-propyl butylamine, diη-propyl n-pentyl amine, diη-propyl
Hexyl amine, diη-propyl octyl amine, diη-propyl (2-ethylhexyl) amine, diisopropyl ethyl amine, diisopropyl n-pro-pyl amine,
Diisopropyl butylamine, diisopropyl amylamine, diisopropyl hexyl amine, diisopropyl octyl amine, diisopropyl (2-ethyl hexyl
Base) amine, di-n-butyl ethylamine, di-n-butyl n-pro-pyl amine, di-n-butyl n-pentyl amine, di-n-butyl hexyl amine, two positive fourths
Base octyl amine, di-n-butyl-(2-ethylhexyl) amine, N-n-butylpyrrolioine, N-sec-butyl pyrrolidine, N-tert-butyl group pyrroles
Alkane, N-n-pentyl pyrrolidine, N, N-dimethylcyclohexylam,ne, N, N-diethyl cyclo-hexylamine, N, N-di-n-butyl cyclo-hexylamine,
N-n-pro-pyl piperidines, N-isopropyl piperidines, N-n-butylpiperidine, N-sec-butyl piperidines, N-tert-butylpiperidin, N-n-pentyl piperazine
Pyridine, N-normal-butyl morpholine, N-sec-butyl morpholine, N-tert-butyl group morpholine, N-n-pentyl morpholine, N-Benzyl-N-ethyl aniline, N-benzyl
Base-N-n-pro-pyl aniline, N-benzyl-N-isopropyl aniline, N-benzyl-N-n-butyl aniline, N, N-dimethyl-p-toluidine, N,
N-diethyl-p-tlouidine, N, N-di-n-butyl para-totuidine, diethylbenzyl amine, diη-propyl benzyl amine, di-n-butyl benzyl
Base amine, diethyl phenyl amine, diη-propyl phenyl amine and di-n-butyl phenyl amine.Preferably tertiary amine be diisopropyl ethyl amine,
Diethyl tert-butylamine, diisopropyl butylamine, di-n-butyl n-pentyl amine, N, N-di-n-butyl cyclo-hexylamine and amyl group are different
The tertiary amine of structure body.Particularly preferred tertiary amine is di-n-butyl n-pentyl amine and the tertiary amine of pentyl isomers.Another preferably has
The tertiary amine of three identical groups is triallylamine.
Furthermore it is preferred that cation be unsubstituted or substituted guanidinium ion.Guanidinium ion very particularly preferably is N, N, N',
N', N'', N''-hexamethyl guanidinium ion.
Furthermore it is preferred that cation be unsubstituted or substituted cholinium ion.
Furthermore it is preferred that cation be unsubstituted or substituted 1,5-diazabicyclo [4.3.0] nonyl-5-alkene (DBN) and
The cation of 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (DBU).
Furthermore it is preferred that cation be unsubstituted or substitutedIon.
Furthermore it is preferred that cation be unsubstituted or substituted sulfonium cation.
In above-mentioned heterocyclic onium cations, preferably imidazolesIon, imidazolineIon, pyridineIon, dihydro pyrrole
AzolesIon and pyrazolesIon.Particularly preferably imidazolesIon.
The anion of described ionic liquid is selected from:
1.) the anion of following formula: F-、Cl-、Br-、I-、BF4 -、PF6 -、CF3SO3 -、(CF3SO3)2N-、CF3CO2 -、
CCl3CO2 -、CN-、SCN-、OCN-；
2.) the anion of following formula: SO4 2-、HSO4 -、SO3 2-、HSO3 -、RcOSO3 -、RcSO3 -；
3.) the anion of following formula: PO4 3-、HPO4 2-、H2PO4 -、RcPO4 2-、HRcPO4 -、RcRdPO4 -；
4.) the anion of following formula: RcHPO3 -、RcRdPO2 -、RcRdPO3 -；
5.) the anion of following formula: PO3 3-、HPO3 2-、H2PO3 -、RcPO3 2-、RcHPO3 -、RcRdPO3 -；
6.) the anion of following formula: RcRdPO2 -、RcHPO2 -、RcRdPO-、RcHPO-；
7.) formula RcCOO-Anion；
8.) the anion of following formula: BO3 3-、HBO3 2-、H2BO3 -、RcRdBO3 -、RcHBO3 -、RcBO3 2-、B(ORc)(ORd)(ORe)
(ORf)-、B(HSO4)4 -、B(RcSO4)4 -；
9.) the anion of following formula: RcBO2 2-、RcRdBO-；
10.) the anion of following formula: HCO3 -、CO3 2-、RcCO3 -；
11.) anion of following formula: SiO4 4-、HSiO4 3-、H2SiO4 2-、H3SiO4 -、RcSiO4 3-、RcRdSiO4 2-、
RcRdReSiO4 -、HRcSiO4 2-、H2RcSiO4 -、HRcRdSiO4 -；
12.) anion of following formula: RcSiO3 3-、RcRdSiO2 2-、RcRdReSiO-、RcRdReSiO3 -、RcRdReSiO2 -、
RcRdSiO3 2-；
13.) anion of following formula:
14.) anion of following formula:
15.) formula RcO-Anion；
16.) anion of following formula: HS-、[Sv]2-、[HSv]-、[RcS]-, wherein v is the positive integer of 2-10.Group Rc、Rd、
ReAnd RfIt is preferably independently of one another:
-hydrogen；
-substituted or unsubstituted alkyl, the most substituted or unsubstituted C1-C30Alkyl, particularly preferably replaces or unsubstituted
C1-C18Alkyl, its can between be separated with at least one hetero atom or containing heteroatomic group；
-substituted or unsubstituted aryl, the most substituted or unsubstituted C6-C14Aryl, particularly preferably replaces or unsubstituted
C6-C10Aryl；
-substituted or unsubstituted cycloalkyl, the most substituted or unsubstituted C5-C12Cycloalkyl；
-substituted or unsubstituted Heterocyclylalkyl, preferably has the substituted or unsubstituted Heterocyclylalkyl of 5 or 6 annular atomses,
1,2 or 3 hetero atoms are also comprised or containing heteroatomic group outside wherein said ring de-carbon annular atoms；
-substituted or unsubstituted heteroaryl, preferably has the substituted or unsubstituted heteroaryl of 5-10 annular atoms, wherein
Also comprise 1,2 or 3 hetero atoms outside described ring de-carbon annular atoms or containing heteroatomic group, described hetero atom selected from oxygen, nitrogen,
Sulfur and NRa；
Wherein, multiple group R is being comprisedc-RfAnion in, in each case two in these groups also and its
A part for the described anion of institute's keyed jointing can be that at least one has the saturated, unsaturated of 1-12 carbon atom or aromatics together
Ring or member ring systems, wherein said ring or member ring systems can comprise 1-5 non-conterminous hetero atom or containing heteroatomic group, described miscellaneous
Atom is preferably selected from oxygen, nitrogen, sulfur and NRa；And wherein said ring or member ring systems be unsubstituted can be maybe substituted.
Preferably anion is Cl-、Br-, formate, acetate, propionate, butanoic acid root, lactate, saccharin root
(saccharinate), carbonate, bicarbonate radical, sulfate radical, inferior sulfate radical, C1-C4Alkyl sulfate, methanesulfonate, toluene sulphur
Acid group, trifluoroacetic acid root, C1-C4Acidic phosphates root and bisulfate ion.
Particularly preferred anion is Cl-、Br-、HCOO-、CH3COO-、CH3CH2COO-, carbonate, bicarbonate radical, sulphuric acid
Root, inferior sulfate radical, tosylate, CH3SO3 -Or CH3OSO3 -。
Especially, described anion is selected from Cl-And Br–。
Appropriate ions liquid in the inventive method can be such as with trade nameCommercially available from BASF SE.
Advantageous chemical compounds in the inventive method is for example:
1-ethyl-3-methylimidazoleChloride (EMIM Cl, Basionic ST80),
1-ethyl-3-methylimidazoleMesylate (EMIM CH3SO3, Basionic ST35),
1-butyl-3-Methylimidazole.Chloride (BMIM Cl, Basionic ST70),
1-butyl-3-Methylimidazole.Mesylate (BMIM CH3SO3, Basionic ST78),
Methylimidazole.Chloride (HMIM Cl, Basionic AC75),
Methylimidazole.Disulfate (HMIM HSO4, Basionic AC39),
1-ethyl-3-methylimidazoleDisulfate (EMIM HSO4, Basionic AC25),
1-butyl-3-Methylimidazole.Disulfate (BMIM HSO4, Basionic AC28),
1-ethyl-3-methylimidazoleAcetate (EMIM Acetate, Basionic BC01),
1-butyl-3-Methylimidazole.Acetate (BMIM Acetate, Basionic BC02).
Particularly preferably 1-ethyl-3-methylimidazoleChloride, 1-butyl-3-Methylimidazole.Chloride, methyl miaow
AzolesChloride, 1-ethyl-3-methylimidazoleAcetate, 1-butyl-3-Methylimidazole.Acetate and mixture thereof.
Those being particularly suitable are 1-butyl-3-Methylimidazole.Chloride and Methylimidazole.Chloride.
Solvent (LM)
The compositions provided in step i) comprises at least one and has under standard conditions (100 DEG C, 1013 millibars) the highest
It it is the solvent (LM) of the boiling point of 120 DEG C.
Solvent (LM) used in step i) is preferably selected from the mixed of water and water and at least one water immiscible organic solvents
Compound.
Preferably water immiscible organic solvents selected from methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, twoAlkane, tetrahydrochysene
Furan and mixture thereof.
Preferably, solvent (LM) used is water-alcohol mixture, particularly water-methanol mixture.
Preferably, use weight ratio to be 10:90-90:10, particularly preferably 25:75-75:25 in step i), be especially
The water of 40:60-60:40 and the mixture of at least one water immiscible organic solvents are as solvent (LM).
It is particularly preferred that solvent (LM) used in step i) is weight ratio is 10:90-90:10, particularly preferably
25:75-75:25, is the water mixture with at least one alcohol of 40:60-60:40 especially.
Especially, solvent (LM) used in step i) be weight ratio be 10:90-90:10, particularly preferably 25:75-
75:25, is the water mixture with methanol of 40:60-60:40 especially.
Preferably, in the compositions of the carbohydrate containing provided in step i), ionic liquids ionic liquids (IL)
It is 99.5:0.5-50:50, particularly preferably 99:1-75:25 with the weight ratio of solvent (LM).
In order to provide the compositions of described carbohydrate containing in step i), can make to comprise the former of described carbohydrate
Material is fully contacted with ionic liquid (IL) and/or solvent (LM).In the method, the raw material of described carbohydrate containing at least portion
Point, preferably completely solvation.If necessary, in advance the raw material of described carbohydrate containing is implemented pre-treatment step to remove not
Soluble component and/or be separated off insoluble component from the compositions of described carbohydrate containing, is then introduced into evaporation
In device.In order to provide the compositions of described carbohydrate containing in the step i), can by the raw material of described carbohydrate containing and
Ionic liquid (IL) and/or solvent (LM) mechanical mixture stirring are to being completely dissolved.
Preferably, in order to provide the compositions of described carbohydrate containing in step i), in being close to entrance vaporizer
Make described at least one ionic liquid (IL) contact with each other with at least one solvent (LM) before." be close to enter vaporizer it
Before " mean from starting described contact until the time entering vaporizer is at most 5 minutes, the most at most 1 minute.Described
Before contact starts, the raw material of described carbohydrate containing can exist only in solvent (LM) or exist only in described ionic liquid
In body, or part is present in solvent (LM) and part is present in described ionic liquid.
Preferably, in order to provide the compositions of described carbohydrate containing in step i), by described ionic liquid (IL)
It is heated above the temperature of ambient temperature (23 DEG C).Preferably, for providing the group of described carbohydrate containing in step i)
The ionic liquid (IL) of compound has at least 50 DEG C, the temperature of preferably at least 75 DEG C.
In specific embodiments, the method for the present invention is for making the compositions dehydration comprising list-and/or oligosaccharide, wherein
In step i):
I1) at least one monosaccharide and/or at least one oligosaccharide are dissolved in water-alcohol mixture；
I2) will be in step i1) in the solution of gained mix with at least one ionic liquid (IL)；
I3) immediately will be in step i2) in gained mixture feed step ii) vaporizer in.
" immediately feed vaporizer in " means from step i2) incorporation time start until this mixture enters evaporation
Time in device is at most 5 minutes, the most at most 1 minute.
Step ii)
Step ii in the inventive method) in, the compositions of step i) is fed in vaporizer and in the temperature raised and
Under the pressure reduced existing carbohydrate is dehydrated and evaporation at least some is formed simultaneously dehydration product and molten
Agent (LM).
As the vaporizer in step i), use the vaporizer with short residence time.Advantageously, it is derived from being formed
The low thermal stress of dehydration product.
Suitably vaporizer is the equipment being generally used for this purpose in principle, and it includes having in the simplest situations can
The container of the heat exchange surface of heating.Preferably, membrane evaporator or short path evaporator are used.Short path evaporator according to
The principle that membrane evaporator is identical is run, but has built-in condenser.Therefore, in short path evaporator, steam is to described cold
The path of condenser is extremely short.Suitably membrane evaporator is falling film evaporator, such as, can additionally have the vertical tube evaportator of tube bank.
Preferably there is the vaporizer of movable internals, the most such as scraper plate on the inwall of vaporizer, produce thin liquid film (scraped film type evaporation
Device, scraper-type vaporizer).These includeOrType membrane evaporator.
According to the present invention, step ii) in vaporizer used be preferably substantially vertically arranged.For feeding step i's)
The evaporator inlet of compositions is preferably placed in the upper area of described vaporizer.Preferably, described evaporator inlet is positioned at this
In the top 1/3rd of vaporizer, particularly in top 1/4th.For removing the evaporator outlet of described liquid discharging
It is positioned in the lower area of described vaporizer.Preferably, described evaporator outlet is positioned in the bottom 1/3rd of this vaporizer,
Particularly in bottom 1/4th.Described evaporator outlet is particular on the bottom of this vaporizer.The compositions of step i) is existed
Forming film when upper area feeds in this vaporizer and is to flow down on sidewall, described film is heated by suitable heater.?
In the method, described at least one there is the solvent of the boiling point being up to 120 DEG C under standard conditions (100 DEG C, 1013 millibars)
At least partly evaporation.Meanwhile, under the reaction condition in this vaporizer, the raw material of described carbohydrate containing is dehydrated.From
This vaporizer takes out and comprises the gaseous state discharging of at least one solvent (LM) described in dehydration product and at least some.Described gaseous state goes out
Material is preferably discharged at the upper area of the vaporizer used by the present invention.Especially, described gaseous state discharging is in the steaming used by the present invention
The top sending out device is discharged.
Available suitable mode, such as, provide heat with steam for described vaporizer.
Temperature in described vaporizer is preferably 100-300 DEG C, particularly preferably 150-250 DEG C.
Pressure in described vaporizer is up to 500 millibars.Pressure in described vaporizer is particularly preferably 250-0.1 milli
Bar, specifically for 100-1 millibar.
The time of staying (based on ionic liquid (IL)) in described vaporizer is 0.1 second to 2 minutes, particularly preferably 1
Second was to 1 minute.
Step iii)
From described vaporizer, take out the gaseous state discharging comprising dehydration product and taking-up comprises at least one ionic liquid described
The liquid discharging of body (IL).
Preferably, in step iii) in the gaseous state spout bag taken out from described vaporizer containing at least 75 weight %, the most excellent
Choosing at least 90 weight %, the solvent (LM) of particular at least 95 weight %, based on the solvent (LM) provided in step i) total
Amount.
Preferably, in step iii) in the gaseous state spout bag taken out from described vaporizer containing at least 75 weight %, the most excellent
Choosing at least 90 weight %, the solvent (LM) of particular at least 95 weight %, based on the solvent (LM) provided in step i) total
Amount.
Preferably, in step iii) in the gaseous state spout bag taken out from described vaporizer containing 0.1 weight %, particularly preferably
At least 0.5 weight %, the dehydration product of particular at least 1 weight %, the gross weight of gaseous state discharging based on condensation.
Preferably, in step iii) in the liquid spout bag taken out from described vaporizer containing at least 90 weight %, the most excellent
Choosing at least 95 weight %, the ionic liquid (IL) of especially at least 99 weight %, based on the ionic liquid provided in step i)
(IL) total amount.
Preferably, in step iii) in from described vaporizer take out liquid discharging there are at most 5 weight %, the most excellent
Choosing at most 1 weight %, the water content of in particular up to 0.5 weight %, gross weight based on described liquid discharging.
Available from described reaction zone liquid spout bag containing a certain proportion of not together with described gaseous state discharging from described evaporation
The product of the raw material of the carbohydrate containing discharged in device.Additionally, also comprise not available from the liquid discharging of described reaction zone
The raw material of the carbohydrate containing of the unreacted ratio discharged from described vaporizer together with described gaseous state discharging.
The ionic liquid (IL) that preferably, there are in described liquid discharging makes in the step i) of the inventive method again
With.In this case, the product of the raw material of existing described carbohydrate containing and the carbon containing water of unreacted ratio
The raw material of compound is typically not critical.
If necessary, described liquid discharging can be carried out at least one purification step and be present in ion with at least part of removing
Residual components in liquid (IL).This includes such as extracting with suitable spe medium such as water.
In another embodiment, by suitable precipitant, described liquid discharging is precipitated, so that being present in institute
State at least some components precipitate in ionic liquid.Precipitation be particularly suited for remove higher molecular weight component, such as polysaccharide and
Higher molecular weight catabolite such as cellulose, hemicellulose etc..Suitably precipitant is well-known to those skilled in the art.
Step iv)
Step iv in the inventive method) in, make to condense and separate available from the gaseous state discharging of described vaporizer, thus
Reclaim dehydration product.
Suitably condenser be those skilled in the art sufficiently known, such as heat exchanger, such as plate type heat exchanger, spiral
Plate type heat exchanger, tube bundle heat exchanger, U-tube heat exchanger.Described condenser selects as requested and designs.Can use total
Body formula condenser, it is possible to use the combination of multiple condensers of series connection.Now, each downstream on described gaseous state discharging flow direction
Condenser preferably runs under than the condenser lower temperature being positioned at more upstream.It is achieved in the gaseous state available from described vaporizer
The fractional condensation of discharging.
Preferably, in described condenser, the gaseous state discharging of described vaporizer is cooled to-30 DEG C to 70 DEG C, preferably-20
DEG C to the temperature of 50 DEG C.
The separation of condensate can be carried out by conventional method known to the person skilled in the art.Preferably, by distillation
Described condensate is separated.Being applicable to the equipment by separated and include distillation column, such as plate column, it may be provided with bubble
Cover, sieve plate, screen tray, irregular implant, orderly implant, valve, side draw etc.；Vaporizer, such as membrane evaporator, falling film evaporation
Device, forced-circulation evaporator, Sambay vaporizer and combinations thereof.
Preferably, described condensate is separated, thus obtains following stream:
D1) rich in the stream of the carbohydrate through dehydration, and
D2) rich in the stream of solvent (LM).
Optionally, can separate available from the discharging in dealkylation region, thus obtain other streams.Such as, if
Use in the method for the invention the mixture of mixture, such as water and at least one water immiscible organic solvents as solvent,
Then D1) and/or D2) fraction can comprise various ingredients, and each component can be separated further by distillation.Or, to by distillation
Separation for, can use and there is the tower of side draw, next door tower or thermal coupling tower, described condensate can be separated into three kinds or more by this
Multiple fraction.
Fraction D1) generally comprise in an amount of from least 50 weight %, particularly preferably at least 75 weight %, particular at least 90 weights
The primary product of amount %.The primary product being present in this fraction particularly depends on hydrocarbon feed used.It is thus possible, for instance when using
Hexose or when mainly comprising the hydrocarbon feed of hexose, it is thus achieved that as the 5-Hydroxymethylfurfural of primary product.
The dehydration product of gained can (according to required purity and application purpose) directly use or in further work-up
And/or use after purification.This includes such as synthetic drug, polymer, macrocyclic compound etc..Obtained by the inventive method
5-HMF can be directly used as or be used as synthetic drug, polymer and the starting point of macrocyclic compound after derivation.Suitably 5-
HMF derivant for example, 2,5-furfuryl group diamidogen, 2,5-furfuryl group diisocyanate and 5-hydroxymethyl furfurylidene ester, it can be used for making
Standby polyester, polyamide and polyurethane.
Can be used further in the step i) of the inventive method by described condensate or its each component recovered solvent (LM).
The present invention is explained in more detail with reference to non-limiting example hereafter.
Embodiment
Fig. 1 shows the equipment for implementing the inventive method.By two bursts of controlled chargings, (wherein one is used for feeding place
The solution of the carbohydrate in solvent (LM) and one be used for feeding ionic liquid (IL)) merge and feed scraper-type evaporation
In device.Scraper-type vaporizer used is to be made up of HC steelVaporizer, it has the vaporizer table of 0.1m2
Face, 4 scraper plates and Normag motor.Top exit is connected with cooler, condensate and vacuum diaphragm pump.Further it is provided that
There is the outlet at bottom collecting container.
Embodiment 1
Described vaporizer is heated to the inner wall temperature of 200 DEG C and scraper rotary rotational speed rate is set as 900rpm.Described steaming
Send out device to run under the vacuum of 1 millibar.By 300g/h butyl methyl imidazolesThe charging of chloride (BMIM chloride) is heated to
80 DEG C, and measure addition together and simultaneously with the charging of 22.3g/h fructose/methanol/water (1:1:1, g/g/g) mixtureIn vaporizer.It is continuously withdrawn the gaseous state discharging of 421.1g/h, condenses at-5 DEG C in cooler and be collected in
Receive in container.By HPLC, condensate is analyzed.2.02g5-HMF/100g being detected, this corresponds to the productivity (base of 8%
In fructose).
Embodiment 2
According to the program of embodiment 1, wherein use Methylimidazole.Chloride (HMIM chloride) is as ionic liquid.
Described vaporizer is heated to the inner wall temperature of 170 DEG C.Muriatic for 300g/h HMIM charging is heated to 80 DEG C and and 44g/
Addition is measured in the charging of h fructose/methanol/water (1:1:1, g/g/g) mixture together and simultaneouslyIn vaporizer.
Detect based on the 5-HMF productivity that fructose is 10.1%.
Claims (38)
1. for the method making the compositions continuous dehydration of carbohydrate containing, comprising:
I) provide and comprise the compositions of following component:
The raw material of-at least one carbohydrate containing, it is selected from list-and/or oligosaccharide,
-at least one ionic liquid, it is selected from 1-ethyl-3-methylimidazoleChloride, 1-ethyl-3-methylimidazoleFirst
Sulfonate, 1-butyl-3-Methylimidazole.Chloride, 1-butyl-3-Methylimidazole.Mesylate, Methylimidazole.Chlorination
Thing, Methylimidazole.Disulfate, 1-ethyl-3-methylimidazoleDisulfate, 1-butyl-3-Methylimidazole.Hydrogen sulfate
Salt, 1-ethyl-3-methylimidazoleAcetate and 1-butyl-3-Methylimidazole.Acetate；With
-at least one has the solvent of the boiling point being up to 120 DEG C under normal pressure (1013 millibars)；
Ii) compositions of step i) fed in vaporizer and make it the temperature of 100-300 DEG C and be up to the pressure of 500 millibars
React under power and evaporate；
Iii) from described vaporizer, take out the gaseous state discharging comprising dehydration product, and taking-up comprises at least one ionic liquid
Liquid discharging；
Iv) make described gaseous state discharging condensation and it is separated described dehydration product；
Wherein the time of staying in described vaporizer be 0.1 second to 2 minutes, based on ionic liquid.
Method the most according to claim 1, wherein the containing of the raw material of the carbohydrate containing of the compositions provided in step i)
Amount is 1-20 weight %, gross weight based on described compositions.
Method the most according to claim 1, wherein the containing of the raw material of the carbohydrate containing of the compositions provided in step i)
Amount is 2-15 weight %, gross weight based on described compositions.
Method the most as claimed in one of claims 1-3, the raw material of wherein said carbohydrate containing is selected from list-and/or two
Sugar.
Method the most according to claim 1, wherein said list-and/or oligosaccharide be selected from:
-aldopentose,
-aldohexose,
-ketohexose,
-derived from the disaccharide of aldopentose, aldohexose, ketohexose and mixture thereof, and
-its mixture.
6. according to the method for claim 3 or 5, wherein said list-and/or oligosaccharide selected from fructose, glucose, sucrose, xylose and
Its mixture.
Method the most as claimed in one of claims 1-3, wherein solvent has with at least one water miscibility selected from water and water
The mixture of machine solvent.
Method the most as claimed in one of claims 1-3, wherein uses water-alcohol mixture as solvent.
Method the most as claimed in one of claims 1-3, wherein uses water-methanol mixture as solvent.
Method the most as claimed in one of claims 1-3, wherein using weight ratio in step i) is 10:90-90:10's
The mixture of water and at least one water immiscible organic solvents is as solvent.
11. methods according to claim 1, wherein use in the step i) weight ratio be 25:75-75:25 water and at least one
The mixture of water immiscible organic solvents is as solvent.
12. methods according to claim 1, wherein use in the step i) weight ratio be 40:60-60:40 water and at least one
The mixture of water immiscible organic solvents is as solvent.
13. methods as claimed in one of claims 1-3, the wherein combination of the carbohydrate containing provided in step i)
In thing, ionic liquid is 99.5:0.5-50:50 with the weight ratio of solvent.
14. methods according to claim 13, wherein in the compositions of the carbohydrate containing provided in step i), ion
Liquid is 99:1-75:25 with the weight ratio of solvent.
15. methods as claimed in one of claims 1-3, wherein in order to provide the combination of carbohydrate containing in step i)
Thing, makes at least one ionic liquid described contact with each other before being close to enter in vaporizer with at least one solvent described.
16. methods as claimed in one of claims 1-3, wherein in order to provide the combination of carbohydrate containing in step i)
Thing, ionic liquid has the temperature of at least 50 DEG C.
17. methods according to claim 16, wherein in order to provide the compositions of carbohydrate containing, ionic liquid in step i)
Body has the temperature of at least 75 DEG C.
18. methods as claimed in one of claims 1-3, for making the compositions dehydration comprising list-and/or oligosaccharide, wherein
In step i):
I1) at least one monosaccharide and/or at least one oligosaccharide are dissolved in water-alcohol mixture；
I2) will be in step i1) in obtain solution mix with at least one ionic liquid；
I3) immediately will be in step i2) in obtain mixture feed step ii) vaporizer in.
19. methods as claimed in one of claims 1-3, wherein in step ii) in use there is the evaporation of short residence time
Device is as vaporizer.
20. methods according to claim 19, wherein in step ii) in use membrane evaporator as vaporizer.
21. methods according to claim 19, wherein in step ii) in use there is scraper-type vaporizer as vaporizer.
22. methods according to claim 1, wherein the time of staying in described vaporizer be 1 second to 1 minute, based on ion
Liquid.
23. methods as claimed in one of claims 1-3, wherein in step ii) in, the temperature in described vaporizer is 150-
250℃。
24. methods as claimed in one of claims 1-3, wherein in step ii) in, the pressure in described vaporizer is 250-
0.1 millibar.
25. methods according to claim 24, wherein in step ii) in, the pressure in described vaporizer is 100-1 millibar.
26. methods as claimed in one of claims 1-3, wherein in step iii) in from described vaporizer take out gaseous state
The spout bag solvent containing at least 75 weight %, total amount based on the solvent provided in step i).
27. methods according to claim 26, wherein in step iii) in from described vaporizer take out gaseous state spout bag contain
The solvent of at least 90 weight %, total amount based on the solvent provided in step i).
28. methods according to claim 26, wherein in step iii) in from described vaporizer take out gaseous state spout bag contain
The solvent of at least 95 weight %, total amount based on the solvent provided in step i).
29. methods according to claim 26, wherein in step iii) in from described vaporizer take out gaseous state spout bag contain
The solvent of at least 99 weight %, total amount based on the solvent provided in step i).
30. methods according to claim 26, wherein in step iii) in from described vaporizer take out gaseous state spout bag contain
The solvent of at least 99.5 weight %, total amount based on the solvent provided in step i).
31. methods as claimed in one of claims 1-3, wherein in step iii) in from described vaporizer take out liquid
The spout bag ionic liquid containing at least 90 weight %, total amount based on the ionic liquid provided in step i).
32. according to the method for claim 31, wherein in step iii) in the liquid spout bag taken out from described vaporizer contain
The ionic liquid of at least 95 weight %, total amount based on the ionic liquid provided in step i).
33. according to the method for claim 31, wherein in step iii) in the liquid spout bag taken out from described vaporizer contain
The ionic liquid of at least 99 weight %, total amount based on the ionic liquid provided in step i).
34. according to the method for claim 31, wherein in step iii) in the liquid spout bag taken out from described vaporizer contain
The ionic liquid of at least 99.5 weight %, total amount based on the ionic liquid provided in step i).
35. methods as claimed in one of claims 1-3, wherein in step iii) in from described vaporizer take out liquid
Discharging has the water content being up to 5 weight %, gross weight based on described liquid discharging.
36. according to the method for claim 35, wherein in step iii) in the liquid discharging taken out from described vaporizer have
It is up to the water content of 1 weight %, gross weight based on described liquid discharging.
37. according to the method for claim 35, wherein in step iii) in the liquid discharging taken out from described vaporizer have
It is up to the water content of 0.5 weight %, gross weight based on described liquid discharging.
38. methods as claimed in one of claims 1-3, are used for
-prepared 5-Hydroxymethylfurfural by fructose, or
-prepared 5-Hydroxymethylfurfural by sucrose, or
-by Furfural Production from Xylose.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11170998.6 | 2011-06-22 | ||
| EP11170998 | 2011-06-22 | ||
| PCT/EP2012/061909 WO2012175584A1 (en) | 2011-06-22 | 2012-06-21 | Method for dehydrating a carbohydrate-comprising composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103619827A CN103619827A (en) | 2014-03-05 |
| CN103619827B true CN103619827B (en) | 2016-08-24 |
Family
ID=46321029
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280029097.8A Expired - Fee Related CN103619827B (en) | 2011-06-22 | 2012-06-21 | Make the method that the compositions of carbohydrate containing is dehydrated |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP2723726A1 (en) |
| JP (1) | JP2014517052A (en) |
| CN (1) | CN103619827B (en) |
| AR (1) | AR086710A1 (en) |
| BR (1) | BR112013032556A2 (en) |
| CA (1) | CA2837782A1 (en) |
| RU (1) | RU2608609C2 (en) |
| TW (1) | TWI548644B (en) |
| UY (1) | UY34159A (en) |
| WO (1) | WO2012175584A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9156802B2 (en) | 2011-12-13 | 2015-10-13 | Basf Se | Separating off 5-hydroxymethylfurfural (HMF) from reaction solutions by steam distillation |
| WO2016207025A1 (en) | 2015-06-24 | 2016-12-29 | Basf Se | Method for synthesizing and separating hmf |
| US9321744B1 (en) | 2015-06-26 | 2016-04-26 | Industrial Technology Research Institute | Method for preparing 2,5-furan dicarboxylic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333200A (en) * | 2008-08-06 | 2008-12-31 | 淮北民生化工科技有限公司 | Method for synthesizing 5-hydroxymethyl-furfural |
| CN101809010A (en) * | 2007-09-07 | 2010-08-18 | 福兰尼克斯科技公司 | hydroxymethylfurfural ethers from sugars or hmf and mixed alcohols |
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|---|---|---|---|---|
| FR2462433A1 (en) * | 1979-08-03 | 1981-02-13 | Bertin & Cie | IMPROVEMENTS IN PROCESSES AND EQUIPMENT FOR OBTAINING FURFURAL FROM PLANT MATERIALS |
| DE19917178A1 (en) * | 1999-04-16 | 2000-10-19 | Karl Zeitsch | Production of furfural from sulfite waste liquor involves heating by direct injection of steam, reaction by boiling under pressure, using easily separated ancillary, and complete vaporization by cooling and depressurization |
| DE10202838A1 (en) | 2002-01-24 | 2003-08-07 | Basf Ag | Separation of acids from reaction mixtures by means of an auxiliary base that forms a liquid salt with the acid to result in two non-miscible phases with the product or solution of the product in a suitable solvent |
| US7393963B2 (en) * | 2004-12-10 | 2008-07-01 | Archer-Daniels-Midland Company | Conversion of 2,5-(hydroxymethyl)furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor |
| US7939681B2 (en) * | 2006-08-07 | 2011-05-10 | Battelle Memorial Institute | Methods for conversion of carbohydrates in ionic liquids to value-added chemicals |
| EP2126104A1 (en) | 2007-01-23 | 2009-12-02 | Basf Se | Method for producing glucose by enzymatic hydrolysis of cellulose that is obtained from material containing ligno-cellulose using an ionic liquid that comprises a polyatomic anion |
| BRPI0806912A2 (en) | 2007-01-23 | 2014-04-29 | Basf Se | PROCESSES TO PREPARE GLUCOSE FROM CELLULOSTIC MATERIAL, AND TO PREPARE A MICROBIAN METABOLISM PRODUCT AT LEAST TWO CARBON AToms |
| PT103684A (en) * | 2007-03-09 | 2008-09-09 | Pedro Manuel Brito Da Silva Correia | LIQUID BIOFUELS CONSTITUTED BY DIHYDROXYMETHYLFURAN, PROPANOL AND ITS PRODUCTION PROCESS FROM POLYOLES OF AGRICULTURAL ORIGIN |
| DE102008009933A1 (en) * | 2008-02-18 | 2009-08-20 | Friedrich-Schiller-Universität Jena | Preparing 5-hydroxymethylfurfural, useful e.g. to manufacture pharmaceutical products such as fungicides, comprises thermally reacting carbohydrates in ionic liquid and discharging formed 5-hydroxymethylfurfural using extracting agent |
| US8110667B2 (en) * | 2008-04-28 | 2012-02-07 | Battelle Memorial Institute | Method for conversion of carbohydrate polymers to value-added chemical products |
| EP2315757A4 (en) * | 2008-06-18 | 2011-11-02 | Agency Science Tech & Res | Production of hydroxymethylfurfural |
| EP2145872A1 (en) * | 2008-07-19 | 2010-01-20 | Cognis IP Management GmbH | Method for dehydrating alcohols |
| SI2449057T1 (en) * | 2009-07-01 | 2021-11-30 | Circa Group Pty Ltd | Method for converting lignocellulosic materials into useful chemicals |
| JP2011184420A (en) * | 2010-03-11 | 2011-09-22 | Univ Of Tokyo | Method for producing monosaccharide |
| CN101811066A (en) * | 2010-05-14 | 2010-08-25 | 天津大学 | Catalyst for synthesizing 5-hydroxymethylfurfural by hexose dehydration and method for synthesizing 5-hydroxymethylfurfural |
-
2012
- 2012-06-21 CA CA 2837782 patent/CA2837782A1/en not_active Abandoned
- 2012-06-21 EP EP12728590.6A patent/EP2723726A1/en not_active Withdrawn
- 2012-06-21 BR BR112013032556A patent/BR112013032556A2/en not_active IP Right Cessation
- 2012-06-21 AR ARP120102227 patent/AR086710A1/en unknown
- 2012-06-21 CN CN201280029097.8A patent/CN103619827B/en not_active Expired - Fee Related
- 2012-06-21 JP JP2014516334A patent/JP2014517052A/en active Pending
- 2012-06-21 RU RU2014101649A patent/RU2608609C2/en not_active IP Right Cessation
- 2012-06-21 WO PCT/EP2012/061909 patent/WO2012175584A1/en unknown
- 2012-06-22 UY UY34159A patent/UY34159A/en unknown
- 2012-06-22 TW TW101122549A patent/TWI548644B/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101809010A (en) * | 2007-09-07 | 2010-08-18 | 福兰尼克斯科技公司 | hydroxymethylfurfural ethers from sugars or hmf and mixed alcohols |
| CN101333200A (en) * | 2008-08-06 | 2008-12-31 | 淮北民生化工科技有限公司 | Method for synthesizing 5-hydroxymethyl-furfural |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2837782A1 (en) | 2012-12-27 |
| BR112013032556A2 (en) | 2016-08-16 |
| AR086710A1 (en) | 2014-01-15 |
| EP2723726A1 (en) | 2014-04-30 |
| RU2608609C2 (en) | 2017-01-23 |
| RU2014101649A (en) | 2015-07-27 |
| TW201307377A (en) | 2013-02-16 |
| UY34159A (en) | 2013-01-03 |
| CN103619827A (en) | 2014-03-05 |
| JP2014517052A (en) | 2014-07-17 |
| TWI548644B (en) | 2016-09-11 |
| WO2012175584A1 (en) | 2012-12-27 |
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